Air brake tubing and compositions for making the same

ABSTRACT

Air brake tubing is provided having an air brake tube body comprising at least one layer formed from a composition comprising a copolyester, polyethylene terephthalate or polybutylene terephthalate; and a thermoplastic polyurethane.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.17/385,411, filed Jul. 26, 2021, which is a continuation of U.S.application Ser. No. 16/797,645, filed Feb. 21, 2020, now issued as U.S.Pat. No. 11,105,445, which is a continuation of U.S. application Ser.No. 15/698,388, filed Sep. 7, 2017, now issued as U.S. Pat. No.10,571,050, which is a continuation application of U.S. application Ser.No. 14/035,424, filed Sep. 24, 2013, now issued as U.S. Pat. No.9,759,353, which claims the benefit of U.S. Provisional Application No.61/704,835, filed Sep. 24, 2012, and U.S. Provisional Application No.61/768,788, filed Feb. 25, 2013, the entire contents of each of which isincorporated herein by reference.

FIELD

Air brake tubing is provided having an air brake tube body comprising atleast one layer formed from a composition comprising a copolyester,polyethylene terephthalate or polybutylene terephthalate; and athermoplastic polyurethane.

BACKGROUND

Heavy-duty vehicles are typically equipped with air brakes operated bycompressed air that is lead through a system of air brake hoses andvalves to the brakes. Connecting multiple trailers on vehicles such astrucks, trailers and semi-trailers to the brake system may beconveniently done using flexible air brake tubing that can be eithercoiled or straight. However, the conditions of the road and safetyconcerns place many requirements on the tubing that is exposed to theenvironment.

Even in normal use, air brake tubing is often subject to environmentaland mechanical stresses. Therefore, to ensure safe operation ofvehicles, air brake tubing is subject to various government and industryregulations. The quality and performance of air brake tubing iscontrolled, for example, by SAE Standard J2494 (Push-To-Connect TubeFittings for Use in the Piping of Vehicular Air Brake), SAE StandardJ1402 (Automotive Air Brake Hose and Hose Assemblies), SAE Standard J844(Nonmetallic Air Brake System Tubing), SAE Standard J2547 (NonmetallicAir Brake System Tubing), and SAE Standard J1131 (PerformanceRequirements for SAE J844 Nonmetallic Tubing and Fitting Assemblies Usedin Automotive Air Brake Systems), as well as NHSA/DOT FMVSS 106 (49C.F.R. § 571.106).

Air brake tubing sizes can vary with slightly different requirements foreach size. For example, acceptable tubing sizes include outer diameter(O.D.) ⅛ inch, 5/32 inch, 3/16 inch, ¼ inch, 5/16 inch, ⅜ inch, ½ inch,⅝ inch and ¾ inch, with corresponding nominal inside diameter (I.D.) of0.156, 0.187, 0.218. 0.281. 0.343, 0.406, 0.531, 0.656 and 0.800 inches.Typically, air brake tubing with an O.D. < 5/16 inch is type Anon-reinforced tubing, and above ⅜ inch O.D. is type B reinforcedtubing.

In the past air brake hoses have most commonly been manufactured frompolyamides such as polyamide 11, polyamide 12 or polyamide 6,copolyesters, or polyamide/copolyester alloys as taught by, for example,U.S. Pat. No. 6,670,004 and U.S. Patent Application Publication No.2007/0087150 A1. One problem with tubing prepared exclusively frompolyamide, for example, PA12, is meeting SAEJ844/DOT FMVSS 571.106 coldtemperature impact testing requirements, such as those described insections 11.3.10 and 11.3.11 of DOT standards, and section 9.10 in SAEstandard.

Alternative tubing composition constructions have been explored due toglobal supply shortages of polyamides. Many tubing manufacturers haveturned to the use of copolyesters; however, most commercially availablecopolyesters require further manipulation in order to meet relevant SAEand DOT requirements. For example, tubing formed from a copolyestersalone, or even a blend of two different copolyesters of differentdurometers, can come close to failing the SAEJ844 stiffness test. Inaddition, the all copolyester design suffered from limited customeracceptance compared to the previously proven polyamide design. Priorattempts at resolving these problems resulted in tubing formed from ablend of copolyester and polyamide that improved tubing stiffness, butcold temperature impact performance was inconsistent from lot to lot.Other disadvantages of air brake hoses formed from apolyamide/copolyester blends include poor chemical resistance, andmoisture issues.

It would be beneficial to provide a composition for making air brakehoses that meets all of the performance requirements and utilizesmaterials that are cost effective and widely available.

SUMMARY

Air brake tubing is provided comprising an air brake tube body having atleast one layer formed from a composition comprising copolyester,polyethylene terephthalate and/or polybutylene terephthalate; andthermoplastic polyurethane. In some embodiments, the air brake tubingcomposition further comprises polyamide. In some embodiments, the airbrake tubing meets all SAE/DOT requirements for air brake hoses.

In some embodiments, tubing is provided that is suitable for use inpneumatic or hydraulic applications, the tubing formed from acomposition comprising about 15-75% by weight copolyester, polyethyleneterephthalate or polybutylene terephthalate or combinations thereof; andabout 15-75% by weight thermoplastic polyurethane. In some embodiments,the tubing is air brake tubing.

As used herein the term “air brake tube body” is defined as a tube bodycapable of meeting the performance requirements of one or more of SAEJ844, SAE J2547 and DOT FMVSS 106 standards.

In some embodiments, the air brake tubing is capable of meeting theperformance requirements of SAE J844, SAE J2547 and DOT FMVSS 106.

In some embodiments, the air brake tubing is mono-wall construction. Insome embodiments, the tube body comprises reinforcement. In someembodiments, the air brake tubing has a multi-layer construction.

In some embodiments, the air brake tubing body comprises at least onelayer formed from a composition comprising about 15-75 wt % copolyesteror polybutylene terephthalate; or about 40-50 wt % copolyester orpolybutylene terephthalate; and about 15-75% by weight polyurethane. Insome embodiments, the composition comprises about 0-10% by weightpolyamide.

In some embodiments, the disclosure provides tubing suitable for use inpneumatic or hydraulic applications, the tubing formed from acomposition comprising about 15-75% by weight copolyester, polyethyleneterephthalate or polybutylene terephthalate or combinations thereof; andabout 15-75% by weight polyurethane. In some embodiments, the tubing issuitable for use in vehicle air brake hoses. In some embodiments, thetubing is an air brake hose is capable of meeting the performancerequirements of SAE J844, SAE J2547 and DOT FMVSS 106. In someembodiments, the tubing comprises about 30-60% by weight copolyester,polyethylene terephthalate, polybutylene terephthalate or combinationsthereof. In some embodiments, the tubing comprises about 40-50% byweight copolyester, polyethylene terephthalate, polybutyleneterephthalate or combinations thereof; and about 30-60% by weightpolyurethane.

In some embodiments, the tubing is formed from a composition comprisingabout 40-50 wt % by weight polyurethane. In some embodiments, thecomposition comprises about 0-50% wt %; 1-15 wt %; 3-12 wt %; or about5-10 wt % polyamide. In some embodiments, the composition is a blend,alloy or copolymer.

Modifications and variations can be made to the embodiments withoutdeparting from the spirit and scope of the disclosure.

BRIEF DESCRIPTION OF FIGURES

FIG. 1 is a schematic drawing of an air brake system according to anembodiment.

FIG. 2A shows copolyester/PET/PBT concentration ranges used incompositions for forming an airbrake tubing body layer.

FIG. 2B shows copolyester/PET/PBT hardness ranges used in compositionsfor forming an airbrake tubing body layer.

FIG. 2C shows thermoplastic polyurethane concentration ranges used incompositions for forming an airbrake tubing body layer.

FIG. 2D shows thermoplastic polyurethane hardness ranges used incompositions for forming an airbrake tubing body layer.

FIG. 2E shows polyamide concentration ranges used in compositions forforming an airbrake tubing body layer.

FIG. 2F shows plasticizer concentration ranges used in compositions forforming an airbrake tubing body layer.

FIG. 3A shows an embodiment of mono-wall air brake tubing.

FIG. 3B shows an embodiment of reinforced air brake tubing.

FIG. 3C shows an embodiment of air brake tubing with multi-layerconstruction.

FIG. 4 is a schematic drawing of an extrusion system used to make theair brake tubing according to an embodiment.

DETAILED DESCRIPTION

The present application relates to tubing suitable for use in air brakesystems and other pneumatic or hydraulic applications and to materialcompositions for making the same. In particular, the present applicationrelates to materials suitable for Type A (non-reinforced) and Type B(reinforced) air brake tubing.

Polymeric air brake tubing comprising one or more layers formed from acomposition comprising (a) one or more of a copolyester, polyethyleneterephthalate and/or polybutylene terephthalate; and (b) polyurethane isprovided. In some embodiments, the air brake tubing comprises at leastone layer formed from a composition comprising (a) one or more of acopolyester, polyethylene terephthalate and/or polybutyleneterephthalate; (b) a polyurethane; and (c) a polyamide. The compositionscan be used for manufacturing mono-layer tubing, reinforced tubing ormulti-layer tubing. The polymeric air brake tubing provided herein meetsperformance requirements specified in SAE and DOT standards.

FIG. 1 shows an example of an air brake system 10 used in vehicles.Compressed air is generated in the air compressor 11 and dried using anair dryer 12. Dried air can be stored in one or more compressed airstorage/supply tanks 13. When brakes are applied by pressing on the footvalve 14, compressed air is led to the brake chambers 18 through airbrake hoses 16 (i.e. air brake tubing). Alternatively, brakes can beapplied by a hand control valve (e.g., the park brake). The compressedair can also be regulated by various other modulators and valves 15 suchas control valves, protection valves, safety release valves and loadsensing valves (not shown). The brake system 10 of a vehicle may also beconnected to the brake system of another vehicle unit such as a trailer.When in use, air brake hoses are exposed to wear and tear, and the roadconditions, such as heat, cold and moisture, and various chemicals suchas road salt, oil, etc.

Air brake tubing is typically constructed of a thermoplastic core innerlayer that may optionally be reinforced by a layer of wound or braidedmaterial and protected by an outer layer that can withstand abrasion andwear. The possible materials and construction used to make air braketubing are limited by the requirement to withstand multiple stressors,including environmental and mechanical stress factors as articulated inthe regulatory requirements set by the SAE (such as SAE Standard J844and J2547) and DOT (such as DOT FMVSS 106). The test parameters alongwith the required limits for 1/4 inch tubing are listed in TABLE 1. Forexample, the tubing must meet particular requirements for withstandingextreme temperatures and exposure to moisture and chemicals and yetremain pliable and impact and burst resistant. Some other testparameters include, for example, ambient burst strength, moistureabsorption, zinc chloride resistance, stiffness, and tensile strength.In order to pass the requirements for the Boiling Water Conditioning andTensile Strength (hot pull) test, the test criteria allows for meetingeither the minimum 50 lbf (L) or minimum % elongation of 50% (L)specifications. Polyamide (“PA”) 12 is a common material formanufacturing air brake tubing, but when used by itself in a singlelayer (e.g., a mono-wall tube), PA12 may not have optimal coldtemperature impact resistance. On the other hand, copolyester, anotherpopular material for air brake tubing, is relatively inflexible, and aconstruction using copolyester only may have difficulty meeting thestiffness requirements.

TABLE 1 DOT/SAE Standard Test Limits. DOT (D)/ Requirements for ¼ inchO.D. tube Test SAE (S) (L = lower limit, U = upper limit) Constriction DI.D. > 66 of nominal, Pass/Fail High T. Cond. & Dimensional Stability DDimensions shall not exceed Boiling Water Cond. & Dimensional Stabilityspecified values, Pass/Fail Ambient Burst Strength D & S 1206 psi (L)Moisture Absorption and Burst Strength, psi D & S 2% (U) and 960 psi (L)Ultraviolet Light Resistance D & S 960 psi (L) Low/Cold T. Flexibility D& S Pass/Fail High T. Flexibility & Burst Strength D & S 960 psi (L)High T. Resistance & Burst Strength D & S 960 psi (L) High T. Cond. (72h) & Cold T. Impact D 960 psi (L) High T. Cond. (24 h) & Cold T. ImpactS 960 psi (L) Boiling Water Cond. & Cold T. Impact D & S 960 psi (L)Zinc Chloride Resistance D & S No visible cracks, Pass/Fail MethylAlcohol Resistance D & S No visible cracks, Pass/Fail High T. Cond. &Collapse Resistance D & S 20% (U) Ozone Resistance D No visible cracks,Pass/Fail Oil Resistance D 960 psi (L) Tensile Strength D 50 lbf (L)Boiling Water Cond. & Tensile Strength (hot D & S 50 lbf (L) or 50% (L)pull), lbf Thermal Cond. & Tensile Strength (Conditioned), D & S 50 lbf(L) and 50% (L) lbf Vibration Resistance D & S 50 sccm @ 1M cycles, 25sccm after 1 h rest End Fitting Retention D & S 960 psi (L) ThermalCond. & End Fitting Retention D & S No rupturing or disconnect,Pass/Fail End Fitting Serviceability D & S Leakage < 25 sccm End FittingCorrosion Resistance D No base metal corrosion, Pass/Fail Stiffness S 2lbs (U) Adhesion S N/A Heat Aging Adhesion S N/A T. = Temperature, Cond.= Conditioning

The shortcomings of the materials typically used for making air brakehoses can be overcome by combining polymers with different properties ina composition (e.g., a blend, alloy or co-polymer) that fulfills theregulatory requirements set by the SAE and DOT. According to anembodiment, a composition suitable for tubing used in air brake systemsand other pneumatic or hydraulic applications may comprise a combinationof copolyester, polyethylene terephthalate and/or polybutyleneterephthalate and thermoplastic polyurethane and optionally polyamide(e.g., impact modified polyamide). The combination of polymers benefitsfrom the better processability and temperature performance ofcopolyester, polyethylene terephthalate and/or polybutyleneterephthalate and the flexibility and hydrolytic stability ofpolyurethane. Referring to FIGS. 2A through 2F, ranges of components ofcompositions according to embodiments are shown.

As shown in FIG. 2A, in some embodiments, the composition comprisesapproximately 15-75 wt %, or approximately 30-60 wt %, or approximately40-50 wt % of one or more copolyester, polyethylene terephthalate (PET)and/or polybutylene terephthalate (PBT), compared to the total weight ofthe unfilled composition.

In some embodiments, the composition comprises one or more copolyesters.Copolyesters are selected from thermoplastic copolyester basedelastomers. In some embodiments, the composition comprises a copolyestercombination of a hard segment of polyester (PBT) and a soft segment ofpolyethers or polyester. In some embodiments, the copolyester can impartstiffness under high temperature conditions. In some embodiments, thecopolyester does not contain an elastomer. In some embodiments, thecopolyester is an extrusion grade copolyester elastomer. In someembodiments, the copolyester is selected from a commercially availablecopolyester. In some embodiments, the copolyester is selected from acommercially available copolyester, for example, from Dupont or DSMEngineering Plastics, Inc. In some embodiments, the copolyester isselected from EM630-H, 63 Shore D hardness, extrusion grade copolyesterelastomer, Arnitel® (DSM Engineering Plastics, Inc.); EM630, 60 Shore D,extrusion grade copolyester elastomer, Arnitel® (DSM EngineeringPlastics, Inc.); and EM740, 74 Shore D, extrusion grade copolyesterelastomer, Arnitel® (DSM Engineering Plastics, Inc.).

In some embodiments, the composition comprises one or more polybutyleneterephthalates (PBT). In some embodiments, the PBT is a partiallycrystalline saturated polyester based on polybutylene terephthalate(PBT). In some embodiments, the PBT is a commercially PBT such as anArnite® (DSM) or Ultradur® PBT (BASF). The PBT can be unreinforced, orreinforced, for example, with glass fiber, or mineral reinforced. Insome embodiments, the PBT is impact modified.

In some embodiments, the composition comprises one or more polyethyleneterephthalates (PET). Polyethylene terephthalate is a copolymerpolyester. PET can be prepared from, for example, an esterificationreaction between terephthalic acid and ethylene glycol; or bytransesterification between, for example, ethylene glycol and dimethylterephthalate. The polyethylene terephthalate can be a commerciallyavailable polyethylene terephthalate. In some embodiments, thecomposition comprises a polyethylene terephthalate such as Array™ 9921polyethylene terephthalate (DAK Americas).

Copolyesters, polyethylene terephthalates and/or polybutyleneterephthalates of varying hardness can be used as shown in FIG. 2B. Insome embodiments, the copolyester, polyethylene terephthalate and/orpolybutylene terephthalate exhibits a durometer reading of about 30D-80Don the Shore scale, or about 40D-74D, or about 47D-74D, or about55D-74D, or about 63D-74D, or about 63D. In some embodiments, thecopolyester, polyethylene terephthalate and/or polybutyleneterephthalate exhibits a durometer reading of about 74D. In someembodiments, two known durometers of copolyester are combined in thecomposition, for example, 63D and 74D. Different types of copolyester,polyethylene terephthalate and/or polybutylene terephthalate or blends,alloys or co-polymers including one or more of such materials may beused.

As shown in FIG. 2C, in some embodiments, the composition comprisesapproximately 15-75 wt %, or approximately 30-60 wt %, or approximately40-50 wt % polyurethane, compared to the total weight of the unfilledcomposition. The polyurethane is a thermoplastic polyurethane (TPU) isselected from one or more TPUs. A polyurethane is a polymer composed oforganic units joined by carbamate (urethane) links. Polyurethanepolymers are generally formed by reacting an isocyanate with a polyol.The isocyanates and polyols contain on average two or more functionalgroups per molecule. Thermoplastic polyurethanes (TPUs) arethermoplastic elastomers that can exist in a molten state when subjectto heat. TPUs consist of linear segmented block copolymers composed ofhard and soft segments. TPUs are formed, for example, from threecomponents: (a) diisocyanates, (b) short chain diols (chain extenders);and (3) long chain bifunctional diols (polyols). The hard block isconstructed from a chain extender and isocyanate and can impart the TPUwith toughness and physical performance properties. The soft block isconstructed from a polyol and an isocyanate and can impart flexibilityand elastomeric character to the TPU. Various TPU properties can includeelasticity, transparency, and resistance to oil, grease, and abrasion.In some embodiments the brake line tubing is formed from a compositioncomprising copolyester, polyethylene terephthalate and/or polybutyleneterephthalate; and a thermoplastic polyurethane. In some embodiments,the polyurethane is a polyether-based polyurethane. In some embodiments,the thermoplastic polyurethane (TPU) is a commercially available TPU. Insome embodiments, the TPU is selected from a commercially availablepolyether-based polyurethane selected from a BASF Elastollan® TPU or aHuntsman TPU. In some embodiments, for example, the TPU is apolyether-based TPU selected from BASF 1164D (Shore D hardness 64), BASF1154D (Shore D hardness 53), Huntsman D64P4777 (Shore D hardness 62) orHuntsman A98P4535 (Shore D hardness 51). In some embodiments, thepolyurethane is a polyester-based polyurethane.

Polyurethanes of varying hardness can be used as shown in FIG. 2D. Forexample, in some embodiments, the polyurethane exhibits a durometerreading of about 51D-74D on the Shore scale, or about 60D-70D, or about64D. Different types of polyurethane may be used, such as for example apolyester or a polyether type or blends, alloys or co-polymers thatinclude polyurethane.

In some embodiments, the composition comprises one or more polyamides(nylon). As shown in FIG. 2E, in some embodiments, the composition mayadditionally comprise approximately 0-50 wt %, or approximately 0-20 wt%, or approximately 0-10 wt %, or approximately 0-5 wt % polyamidecompared to the total weight of the unfilled composition. In otherembodiments, the composition comprises polyamide in approximately 0.1-20wt %, or approximately 1-15 wt %, or approximately 3-12 wt %, comparedto the weight of the total weight of the unfilled composition. In somespecific embodiments, the composition comprises approximately 5 wt %, orapproximately 10 wt % polyamide. Various types of polyamide or blends,alloys or co-polymers that include one or more polyamides may be used.For example, the polyamide may include one or more of the followingpolyamides: PA612, PA6, PA12, PA66, PA610, PA1010, PA1012, PA11, PA12 orPA1212, and may be either plasticized or unplasticized. In someembodiments, the polyamide is an impact modified polyamide. In someembodiments, the polyamide is selected from PA6, PA612, or PA610. Insome embodiments, the polyamide is an impact modified PA612. In someembodiments, the PA is a commercially available PA. In some embodiments,the PA is a commercially available PA612, such as Grilamid® 2D,(EMS-Grivory); In some embodiments, the PA is a commercially availablePA610, such as Grilamid® 2S, (EMS-Grivory), or Ultramid® S Balance(BASF). In some embodiments, the PA is a regrind, or recycled PA.

In some embodiments, the composition comprises other additives such asheat and light stabilizers, impact modifiers, lubricants, wettingagents, antioxidants, pigments, dyes, colorants, colorings, oropacifying agents such as for coloring-coding of the tubing,luminescents, light reflectants, chain extending oils, tackifiers,blowing agents, foaming or anti-foaming agents, reinforcements such asglass, carbon, or textile fibers, and fire retardants such ashalogenated compounds, metal oxides and salts, The additives may be inliquid, powder, particulate, flake, fiber, or other form. The impactmodifier may be a maleic anhydride (MAH) grafted polyolefin (Fusabond®,Dupont), or an ethylene/methacrylic copolymer-based ionomer resin suchas Suryln®, (DuPont, Wilmington, Del.), or other ethylene copolymerresin which may be a high-molecular-weight copolymer resin such as anEVACO (ethylene/vinyl acetate/carbon monoxide), EBACO (ethylene/butylacrylate/carbon monoxide), or EnBAGMA (ethylene/n-butylacrylate/glycidyl methacrylate) terpolymer resin (Elvaloy®, Dupont). Theheat age stabilizer, in turn, may be a hindered amine, or a proprietaryadditive such as “E1” from DSM Engineering Plastics (Evansville, Ind.).Typically, the optional additives are blended or otherwise admixed withthe composition, and may comprise between about 0.01 wt % and 10 wt %;or between about 0.05 wt % and 5 wt %; or between about 0.1 wt % and 3wt %.

In some embodiments, a plasticizer can be employed to increaseflexibility and cold impact resistance. In some embodiments, theconcentration of plasticizer in the composition may be very low. Forexample, as shown in FIG. 2F, the composition may comprise approximately0-8 wt %, or approximately 0-4 wt %, or as little as approximately 0-1wt % plasticizer. In some embodiments, the composition comprises aplasticizer at approximately 0.1-8 wt %, or approximately 0.3-6 wt %, orapproximately 0.5-4 wt % compared to the weight of the unfilledcomposition. Conventional plasticizers known in the art may be used.

In some embodiments, the air brake tubing composition is unfilled. Insome embodiments, the composition comprises one or more fillers. In someembodiments, the composition comprises one or more fillers selected formintercalated graphite particles, borates, siloxanes, phosphates, glass,hollow or solid glass or elastomeric microspheres, silica, silicates,mica, carbon black and the like. Typically, the optional fillers areblended or otherwise admixed with the base polymeric material, and maycomprise between about 0.1% and 80% by weight compared to the weight ofthe unfilled composition.

The FIGS. 3A through 3C show various embodiments of air brake tubing 20.The composition can be used to make one or more layers or wallthicknesses to be used in tubing. A tubing layer comprised of thecomposition can be used to make a mono-wall tube/hose or can beincorporated into a hose having multiple layers. For example, referringto FIG. 3A, tubing 20 made from the composition can be constructed asmono-wall (i.e. single layer) tubing 21 that meets the size andperformance requirements of SAE Standards J844 and J2547, and DOT FMVSS106. According to embodiments, the tubing may comprise a single layer ofthe composition and may be formed from a composition comprising, forexample, approximately 15-75 wt %, 30-60 wt %, or 40-50 wt %copolyester, polyethylene terephthalate and/or polybutyleneterephthalate; approximately 15-75 wt %, 30-60 wt %, or 40-50 wt %polyurethane; and approximately 0-50 wt %, 0-20 wt %, 0-10 wt %, or 0-5wt % polyamide.

In embodiments, air brake tubing is provided with outer diameter (O.D.)⅛ inch, 5/32 inch, 3/16 inch, ¼ inch, 5/16 inch, ⅜ inch, ½ inch, ⅝ inchand ¾ inch, with corresponding nominal inside diameter (I.D.) of 0.156,0.187, 0.218. 0.281. 0.343, 0.406, 0.531, 0.656 and 0.800 inches.Typically, air brake tubing with an O.D. < 5/16 inch is type Anon-reinforced tubing, and above ⅜ inch O.D. is type B reinforcedtubing. In some embodiments, the air brake tubing is a monolayer, orcomprises two or more, three or more, four or more, or five or morelayers. In some embodiments, the air brake tubing is non-reinforced. Insome embodiments, the air brake tubing comprises a reinforcement layer.

Air brake tubing is provided comprising at least one layer formed from acomposition comprising copolyester, polyethylene terephthalate and/orpolybutylene terephthalate; and polyurethane. In certain embodiments,the composition can be a co-polymer, alloy or blend. In someembodiments, the composition comprises one or more of a copolyester,polyethylene terephthalate and/or polybutylene terephthalate ofdifferent Shore A hardness. For example, the copolyester, polyethyleneterephthalate and/or polybutylene terephthalate may have a durometerreading of about 30D-80D on the Shore scale, or about 40D-74D, or about47D-74D, or about 55D-74D, or about 63D-74D, or about 63D and thepolyurethane may have a durometer reading of about 54D-74D on the Shorescale, or about 60D-70D, or about 64D, or about 74D. In someembodiments, the composition comprises a medium hardness polymer. Insome embodiments, the composition comprises two or more polymersselected from copolyester, polyethylene terephthalate and/orpolybutylene terephthalate and the polyurethane, such that one polymerwith a higher durometer reading can be used to compensate for anotherpolymer with a lower durometer reading. For example, in someembodiments, the composition comprises a copolyester of 63D hardness anda copolyester of 74D Shore D hardness.

In some embodiments, the brake line tubing is prepared from acomposition comprising about 40-50 wt % copolyester, polyethyleneterephthalate and/or polybutylene terephthalate; and about 40-50 wt %polyurethane. In some embodiments, the brake line tubing is preparedfrom a composition comprising about 40-50 wt % copolyester polybutyleneterephthalate and/or polyethylene terephthalate; about 40-50 wt %polyurethane; and about 1-15 wt % of a polyamide.

In specific embodiments, the brake line tubing is prepared from acomposition comprising about 45-47.5 wt % copolyester, polyethyleneterephthalate and/or polybutylene terephthalate; about 45-47.5 wt %polyurethane; and about 5-10 wt % of polyamide 612.

In some embodiments, brake line tubing comprising at least one layerformed from a composition comprising polybutylene terephthalate andpolyurethane is provided.

In some embodiments, the brake line tubing comprises at least one layerformed from a composition comprising between about 25-40 wt %polybutylene terephthalate; about 50-65 wt % polyurethane; and about3-12 wt % of a polyamide; and about 0.1-3 wt % of a heat and/or lightstabilizer.

In some specific embodiments, the brake line tubing comprises at leastone layer formed from a composition comprising between about 35 wt %polybutylene terephthalate; about 55 wt % polyurethane; about 10 wt % ofa polyamide; and about 0.1-3 wt % of a heat and/or light stabilizer.

In some embodiments, the brake line tubing comprises two or more layers.In some embodiments, the brake line tubing comprises at least two layersincluding a polyamide inner layer and an outer layer prepared from acomposition comprising about 45-50/45-50/0-10 wt ratio ofcopolyester/polyurethane/polyamide. In some specific embodiments, thebrake line tubing includes two layers including a polyamide inner layerand an outer layer prepared from a composition comprising 47.5/47.5/5 wt% ratio of copolyester/polyurethane/polyamide.

In some embodiments, the brake line tubing includes three or more layersincluding an inner and outer layer prepared from a compositioncomprising about 45-50/45-50/0-10 wt. ratio of EM740 copolyester/Hunt64D/PA612 and a PA6 or PA12 middle layer.

Tubing 20 made from the composition may also be reinforced as shown inFIG. 3B. The reinforcement 24 may comprise conventional reinforcementmaterials, such as a wound or braided layer of polyester, nylon oraramid. The composition is also suitable for use in multi-layer tubes asshown in FIG. 3C. Multi-layer tubes may include two or more layers andmay comprise, for example, a core 22 comprised of the composition, awound reinforcement layer 24 and a protective outer layer 26. The outerlayer may be constructed of materials such as polyamide, copolyester,polyethylene terephthalate, polybutylene terephthalate, polyurethane orpolyolefin or blends, alloys or co-polymers thereof. Other compositionsand constructions of multi-layer tubes are also possible.

According to exemplary embodiments, tubing may be made of variouscompositions as shown in TABLES 2-4. For example, air brake tubing ofvarying compositions representing Type A, ¼-inch mono-wall constructionmay be prepared and tested according to SAE J844 and DOT FMVSS 106testing protocols.

Referring to TABLE 2, sample 1 is formed from a composition comprisingbetween 45-55 wt % thermoplastic polyurethane with a hardness of 64D(available from Huntsman Corp., Salt Lake City, Utah; BASF Corp.,Florham Park, N.J.; Lubrizol Corp., Wickliffe, Ohio; Bayer, Morristown,N.J.; or DuPont, Wilmington, Del.) and 45-55 wt % copolyester with ahardness of 74D (available from DSM Engineering Plastics, Birmingham,Mich.; or DuPont). Sample 2 is formed from a composition comprisingbetween 42-52 wt % thermoplastic polyurethane with a hardness of 64D,42-52 wt % copolyester with a hardness of 74D, and 3-8 wt % polyamidePA612 (available from DuPont; EMS-CHEMIE Inc., Sumter, S.C.; A.Schulman, Inc., Akron, Ohio; or Arkema, King of Prussia, Pa.). Sample 3is formed from a composition comprising between 40-50 wt % thermoplasticpolyurethane with a hardness of 64D, 40-50 wt % copolyester with ahardness of 74D, and 5-15 wt % polyamide PA612.

Referring to TABLE 3, test sample 4 is prepared from a compositioncomprising between 50-60 wt % of a polyether-based thermoplasticpolyurethane (TPU) of Shore D hardness 53 (BASF) and approximately40-50% polybutylene terephthalate (PBT) (BASF).

Referring to TABLE 4, test sample 5 is formed from a compositioncomprising between 40-50 wt % TPU, polyether-based thermoplasticelastomer of Shore D hardness 64 (BASF), 40-50 wt % 74 Shore D,extrusion grade copolyester elastomer, Arnitel® (DSM EngineeringPlastics, Inc.) and 5-15 wt % polyamide 612. Test sample 6 is formedfrom a composition comprising between 50-60 wt % TPU, 30-40 wt %thermoplastic copolyester elastomer, stabilized, of 72D Shore D hardness(Hytrel®, DuPont), and 5-15 wt % polyamide 612. Test sample 7 is formedfrom a composition comprising between 45-52 wt % TPU, polyether-basedthermoplastic elastomer (Shore D hardness 64) (BASF), 45-52 wt % 74Shore D, extrusion grade copolyester elastomer, Arnitel® (DSMEngineering Plastics, Inc.), and 3-8 wt % polyamide 612. The testresults of 14 of the most critical test parameters for the exemplarycompositions are shown in TABLES 2-4.

TABLE 2 Air Brake Tubing Performance: Test Samples. Test Test TestSAMPLE 1 SAMPLE 2 SAMPLE 3 Polyurethane 45-55 wt % 42-52 wt % 40-50 wt %Copolyester 45-55 wt % 42-52 wt % 40-50 wt % Polyamide — 3-8 wt % 5-15wt % Specification (U = upper limit, L = lower limit) Ambient BurstStrength 1206 psi (L) 1768 psi 1682 psi 1587 psi Moisture Absorption, %2% (U) 0.60% 0.60% 0.50% Moisture Absorption, psi 960 psi (L) 1514 psi1515 psi 1416 psi Low/Cold T. Flexibility Pass/Fail Pass Pass Pass HighT. Flexibility & Burst 960 psi (L) 1464 psi 1560 psi 1462 psi StrengthHigh T. Cond. (72 h) & Cold 960 psi (L) 1484 psi 1536 psi 1461 psi T.Impact High T. Cond. (24 h) & Cold 960 psi (L) 1580 psi 1650 psi 1513psi T. Impact Boiling Water Cond. & Cold 960 psi (L) 1435 psi 1516 psi1418 psi T. Impact Zinc Chloride Resistance Pass/Fail Pass Pass PassHigh T. Cond. & Collapse 20% (U)  7.1%  8.8%  6.1% Resistance Stiffness2 lbs (U) 1.88 lbs 1.78 lbs 1.83 lbs 120° F. Burst 600 psi (L) 704 psi920 psi 893 psi 260° F. Burst 250 psi (L) 479 psi 781 psi 815 psiTensile Strength 50 lbf (L) 117 lbf 106 lbf 95 lbf Boiling Water Cond. &50 lbf (L) 37 lbf 37 lbf 37 lbf Tensile Strength (hot pull), lbf BoilingWater Cond. & 50% (L)   91%   84%   82% Tensile Strength (hot pull), %Thermal Cond. & Tensile 50 lbf (L) 122 lbf 132 lbf 130 lbf Strength(Conditioned), lbf Thermal Cond. & Tensile 50% (L)  310%  311%  294%Strength (Conditioned), % End Fitting Retention 960 psi (L) 1675 psi1623 psi 1434 psi T. = Temperature, Cond. = Conditioning

TABLE 3 Air Brake Tubing Performance: Comparative and Test Samples.Comparative Comparative Test SAMPLE A SAMPLE B SAMPLE 4 Polyurethane — —50-60 wt % Copolyester — 90 wt % — PBT — — 40-50 wt % Polyamide 100 wt %10 wt % — Specification (U = upper limit, L = lower limit) Ambient BurstStrength 1206 psi (L) 1373 psi 1490 psi 1357 psi Moisture Absorption, %2% (U) 1.0% 0.4% 1.04% Moisture Absorption, psi 960 psi (L) 1485 psi1475 psi 1303 psi Low/Cold T. Flexibility Pass/Fail Pass Pass Pass HighT. Flexibility & Burst 960 psi (L) 1614 psi 1501 psi 1270 psi StrengthHigh T. Cond. (72 h) & Cold 960 psi (L) 1691 psi 1473 psi NT T. ImpactHigh T. Cond. (24 h) & Cold 960 psi (L) 1493 psi 1335 psi 1348 psi T.Impact Boiling Water Cond. & Cold 960 psi (L) 1307 psi 1296 psi 1212 psiT. Impact Zinc Chloride Resistance Pass/Fail Pass Pass Pass High T.Cond. & Collapse 20% (U) 3.4% 6.8% NT Resistance Stiffness 2 lbs (U)1.79 lbs 1.84 lbs 2.53 lbs 120° F. Burst 600 psi (L) 894 psi 875 psi 755psi 260° F. Burst 250 psi (L) 459 psi 493 psi 425 psi Tensile Strength50 lbf (L) 87 lbf 92 lbf 118 lbf Boiling Water Cond. & 50 lbf (L) 46 lbf46 lbf 46 lbf Tensile Strength (hot pull), lbf Boiling Water Cond. & 50%(L)  86% 106%    73% Tensile Strength (hot pull), % Thermal Cond. &Tensile 50 lbf (L) 97 lbf 101 lbf 113 lbf Strength (Conditioned), lbfThermal Cond. & Tensile 50% (L) 159%  296%   205% Strength(Conditioned), % End Fitting Retention 960 psi (L) 1390 psi 1326 psi1309 psi T. = Temperature, Cond. = Conditioning, NT = Not yet Tested

TABLE 4 Air Brake Tubing Performance: Test Samples. Test Test TestSAMPLE 5 SAMPLE 6 SAMPLE 7 Polyurethane 40-50 wt % 50-60 wt % 45-52 wt %PBT 40-50 wt % 30-40 wt % 45-52 wt % Copolyester — — — Polyamide 5-15 wt% 5-15 wt % 3-8 wt % Specification (U = upper limit, L = lower limit)Ambient Burst Strength 1206 psi (L) 1412 psi 1285 psi 1297 psi MoistureAbsorption, % 2% (U) 1.13% 1.30% 1.14% Moisture Absorption, psi 960 psi(L) 1190 psi 1160 psi 1274 psi Low/Cold T. Flexibility Pass/Fail PassPass Pass High T. Flexibility & Burst 960 psi (L) 1524 psi 1342 psi 1337psi Strength High T. Cond. (72 h) & Cold 960 psi (L) 1583 psi 1461 psi1240 psi T. Impact High T. Cond. (24 h) & Cold 960 psi (L) 1685 psi 1425psi 1395 psi T. Impact Boiling Water Cond. & Cold 960 psi (L) 1241 psi1069 psi 1112 psi T. Impact Zinc Chloride Resistance Pass/Fail Pass PassPass High T. Cond. & Collapse 20% (U)  9.3% 12.5% 10.0% ResistanceStiffness 2 lbs (U) 1.61 lbs 0.95 lbs 1.75 lbs 120° F. Burst 600 psi (L)697 psi 673 psi 701 psi 260° F. Burst 250 psi (L) 406 psi 356 psi 519psi Tensile Strength 50 lbf (L) 98 lbf 89 lbf 103 lbf Boiling WaterCond. & 50 lbf (L) 37 lbf 34 lbf 35 lbf Tensile Strength (hot pull), lbfBoiling Water Cond. & 50% (L)   74%   84%   75% Tensile Strength (hotpull), % Thermal Cond. & Tensile 50 lbf (L) 105 lbf 108 lbf 115 lbfStrength (Conditioned), lbf Thermal Cond. & Tensile 50% (L)  258%  288% 234% Strength (Conditioned), % End Fitting Retention 960 psi (L) 1428psi 1338 psi 1225 psi T. = Temperature, Cond. = Conditioning

TABLE 2 shows performance of Test Samples 1-3 monolayer tubing samplesformed from different compositions comprising copolyester andpolyurethane with or without polyamide. Test Samples 1-3, as shown inTable 2, exhibit similar or improved performance in standard testscompared to current marketed brake line tubing Comparative Sample A(PA12) or Comparative Sample B (Polyester/PA blend), as shown in Table3. In particular, Test Samples 1-3, formed from a composition comprising40-55 wt % thermoplastic polyurethane, 40-55 wt % copolyester and 0-15wt % polyamide, exhibited improved end fitting retention, improvedperformance in boiling water conditioning and cold temperature impact,and improved tensile strength compared to Comparative Samples A and B.

TABLE 3 shows performance of Test Sample 4 shown in Table 3, a monolayertubing sample formed from a composition comprising 50-60 wt %polyurethane and 40-50 wt % polybutylene terephthalate (PBT) compared tocontrol current marketed Comparative Sample A (ECLIPSE®; Eaton, 100%polyamide) or Comparative Sample B (SOLSTICE®; 90 wt % copolyesterblend/10 wt % polyamide), as shown in Table 3. Test Sample 4 approachesthe performance of Comparative Sample A and Comparative Sample B inseveral criteria in the standard tests, as shown in Table 3. Inparticular, Test Sample 4, formed from a composition comprising 50-60 wt% thermoplastic polyurethane and 40-50 wt % PBT, exhibited improvedtensile strength, and improved performance in thermal conditioning andtensile strength (conditioned, lbf) tests compared to ComparativeSamples A and B.

TABLE 4 shows performance of Test Samples 5-7 monolayer tubing samplesformed from different compositions comprising copolyester andpolyurethane with polyamide. Test Samples 5-7, as shown in Table 4,exhibit similar or improved performance in standard tests compared tocurrent marketed brake line tubing Comparative Sample A (PA12) orComparative Sample B (Polyester/PA blend), as shown in Table 3. Inparticular, Test Samples 5-7, formed from compositions comprising 40-60wt % thermoplastic polyurethane; 30-52 wt % copolyester;

and 3-15 wt % polyamide exhibit improved performance in boiling waterconditioning and cold temperature impact test compared to ComparativeSamples A and B.

As shown in TABLES 2-4, improved tensile strength was exhibited by TestSamples 1-3, 5 and 7 as compared to Comparative Samples A and B.Improved end fitting retention was exhibited by Test Samples 1-3 and 5as compared to Comparative Samples A and B.

As shown in TABLES 2-4, improved performance in Thermal Conditioning &Tensile Strength (conditioned) (lbf) was exhibited by Test Samples 1-7compared to Comparative Samples A and B.

An exemplary method for preparing air brake tubing is illustrated inFIG. 4 . Tubing 20 comprised of the composition may be manufactured onan extrusion system 100 as shown in FIG. 4 . The extrusion system 100may include, among other components, a conveyor 110, a hopper 112, anextruder 114 (e.g., an auger or screw type extruder), a control system116, a heating system 118 and a crosshead 120. The components(polyurethane pellets 102, copolyester, polyethylene terephthalateand/or polybutylene terephthalate pellets 104, and optional polyamidepellets 106) used to make the tubing 20 can be metered into a hopper 112using the conveyor 110 controlled by the control system 116. Thecomponents 102, 104, 106 may be in pellet form or any other suitableform. The components 102, 104, and optional 106 can be at leastpartially mixed in the hopper 112 and then fed into the extruder 114where the components 102, 104, and optional 106 are further mixed andheated with heat supplied by one or more heating elements of the heatingsystem 118. The components 102, 104, and optional 106 may be underpressure prior to or when exiting the extruder 114 into the cross head120. The cross head 120 may include a tip and a die (not show) to formthe body of the tubing 20. After the extrusion process the tubing 20 maybe cooled (e.g., by using a cooling bath) and gathered on a take-upreel. Mixing the components 102, 104, and optional 106 and extrudingthem directly into tubing 20 without additional heating steps may bebeneficial because an additional heating step and therefore degradationof the composition can be avoided. Alternatively it may be desirable insome circumstances to mix and extrude the components 102, 104, andoptional 106 to form pellets comprising the composition that can then beformed into tubing 20 at a later time using the extrusion system 100. Incertain examples, the composition can be a co-polymer, alloy or blend.

Air brake tubing of the present embodiments may possess superiorqualities as compared to existing products by having increased burststrength, reduced moisture absorption, improved impact resistance,increased elevated temperature burst strength, increased tensilestrength both before and after thermal conditioning, better fittingretention, lower cost, and may enable the elimination of plasticizersfrom the product.

From the forgoing detailed description, it will be evident thatmodifications and variations can be made without departing from thespirit and scope of the disclosure.

1. A tubing comprising: a tube body comprising at least one layer formedfrom a composition comprising at least one of the group consisting of acopolyester, a polyethylene terephthalate, and a polybutyleneterephthalate; and a thermoplastic polyurethane.
 2. The tubing of claim1, wherein the composition further comprises polyamide.
 3. The tubing ofclaim 1, wherein the tubing is capable of meeting the performancerequirements of SAL J844, SAE J2547 and DOT FMVSS
 106. 4. The tubing ofclaim 1, wherein the tubing has a mono-wall construction.
 5. The tubingof claim 1, wherein the tube body comprises reinforcement.
 6. The tubingof claim 1, wherein the tubing has a multi-layer construction.
 7. Theair brake tubing of claim 1, wherein the composition comprises about15-75 wt %, about 30-60 wt %, or about 40-55 wt % of the copolyester. 8.(canceled)
 9. The tubing of claim 1, wherein the composition comprisesabout 15-75%, about 30-60 wt %, or about 40-55 wt % of the thermoplasticpolyurethane.
 10. The tubing of claim 1, wherein the compositioncomprises about 0-50 wt %, about 0-20%, about 0.1-20 wt %, about 1-15 wt%, or about 3-12 wt % of the polyamide.
 11. A tubing suitable for use inpneumatic or hydraulic applications, the tubing formed from acomposition comprising about 15-75 % by weight, about 30-60% by weight,or about 40-55 wt % of a copolyester, a polyethylene terephthalate, or apolybutylene terephthalate or combinations thereof; and about 15-75%,about 30-60% by weight, or about 40-55 wt % by weight of a thermoplasticpolyurethane.
 12. The tubing of claim 11, wherein the tubing is capableof meeting the performance requirements of at least one of SAE J844, SATJ2547 and DOT FMVSS
 106. 13. (canceled)
 14. The tubing of claim 11,wherein the tubing has a mono-wall construction.
 15. The tubing of claim11, wherein the tubing comprises reinforcement. 16-19. (canceled) 20.The tubing of claim 11, wherein the composition further comprises about0-50%, about 0-20 wt %, about 0.1-20 wt %, about 1-15 wt %, or about3-12 wt % by weight of a polyamide. 21-23. (canceled)
 24. The tubing ofclaim 1, wherein the composition is a blend, alloy or copolymer.
 25. Thetubing of claim 1, wherein the composition is a blend, alloy orcopolymer that further comprises a polyamide.
 26. The tubing of claim 1,wherein the copolyester, polyethylene terephthalate, or polybutyleneterephthalate exhibits a durometer value in a range of about 30d-80D,about 40D-74D, about 47D-74D, about 55D-74d, or about 63D-74D on theShore scale.
 27. The tubing of claim 26, wherein the copolyestercomprises at least two different copolyesters having different durometervalues.
 28. The tubing of claim 1, wherein the thermoplasticpolyurethane exhibits a durometer value in a range of about 51D-74D, orabout 60D-70D on the Shore scale.
 29. The tubing of claim 2, wherein thepolyamide is selected from the group consisting of a PA612, PA6, PA12,PA66, PA610, PA1010, PA1012, PA 11, PA12 or PA1212 polyamide.
 30. Thetubing of claim 29, wherein the composition includes a plasticizer.